Patent GB-605701-A (GB)
Title: Manufacture of vat dyestuffs
IPC: C09B1/42
Filed: 1944-11-01
Abstract: 4 - (41 - Chloro- and 41 - methoxy - phenylsul - phone)-benzene-3-carboxylic acids are obtained by condensing p-toluenesulphochloride with chlorobenzene or anisole respectively, in the presence of aluminium chloride, and oxidizing the methyl group with permanganate.  3 - Phenylsulphonebenzene - 1 - carboxylic acid is obtainable by condensing benzoic acid-m-sulphochloride with benzene, in excess of benzene as solvent, in the presence of aluminium chloride. Specification 580,642 is referred to.ALSO:Vat dyestuffs, which are 1 : 4-diaroylaminoanthraquinones in which at least one (but preferably only one) of the aroyl groups is the residue of a phenylsulphonebenzenecarboxylic acid, and which may contain further substituents (e.g. halogen atoms), are manufactured by aroylating a 1 : 4-diaminoanthraquinone or a 1-aroylamino-4-aminoanthraquinone with a phenylsulphonebenzenecarboxylic acid or a reactive derivative thereof, or, in the case of a 1 - phenylsulphonebenzoylamino-4-aminoanthraquinone, with any aroylating agent, or by condensing a 1 : 4-dihalogenanthraquinone or a 1 - aroylamino - 4 - halogenanthraquinone with a phenylsulphonebenzenecarboxylic acid amide, or, in the case of a 1-phenylsulphonebenzoylamino-4-halogenanthraquinone, with any aromatic acid amide.  The products may be used for dyeing or printing animal fibres and especially vegetable fibres such as cotton or linen, and regenerated cellulose artificial silk and staple fibres, and also superpolyamide fibres, for which purposes the dyestuffs are advantageously employed in the form of their sulphuric acid leuco-ester salts.  In examples: (1) 4-phenylsulphonebenzene-1-carboxylic acid is stirred with thionyl chloride and a trace of pyridine in o-dichlorobenzene, the excess thionyl chloride and some solvent are distilled off, and the mixture is heated with 1-amino-4-benzoylaminoanthraquinone; the 4-phenylsulphonebenzenecarboxylic acid may be replaced by its 41-chloro- or 41-methoxy-derivative or by 3 - phenylsulphonebenzene - 1 - carboxylic acid; (2) 4-phenylsulphonebenzene-1-carboxylic acid or its 41-chloro-derivative is similarly reacted with 1 : 4-diaminoanthraquinone (in the molecular proportions of 2 : 1); (3) 1-(41-phenylsulphonebenzoylamino) -4-benzoylaminoanthraquinone is vatted with sodium hydrosulphite and caustic soda solution and cotton is dyed in the vat with the addition of sodium chloride, and then squeezed, oxidised in the air, rinsed, acidified, again rinsed, and soaped at the boil, yielding a pink dyeing.  Specification 580,642 is referred to.  Samples have been furnished under Sect. 2(5) of the products obtained by treating (A) 1-chloro-4-benzoylaminoanthraquinone with 4-phenylsulphonebenzene - 1 - carboxylic acid amide; (B) 1-amino-4-(p-chlorobenzoyl)-aminoanthraquinone with 4-phenylsulphonebenzene-1-carboxylic acid chloride; (C) 1-benzoylamino - 4 - amino - 6 - chloroanthraquinone similarly; (D) 1-amino-4-(p-phenylsulphonebenzoylamino)-7-chloroanthraquinone with benzoyl chloride.  1-Benzoylamino - 4 - amino - 3 - chloroanthraquinone is obtainable by benzoylating 1-amino-4- nitro-6-chloroanthraquinone and reducing the nitro group.  1 - Amino - 4 - (p - phenylsulphonebenzoylamino)-7-chloroanthraquinone is obtainable by treating 1-amino-4-nitro-6-chloroanthraquinone with 4 - phenylsulphonebenzene - 1 - carboxylic acid chloride and reducing the nitro group, e.g. with phenylhydrazine in o-dichlorobenzene. 1-Amino-4-nitro-3-chloroanthraquinone is obtainable by heating 1-amino-6-chloroanthraquinone with oxalic acid and nitrating the resulting oxaminic acid in concentrated sulphuric acid.  The Specification as open to inspection under Sect. 91 comprises also the manufacture of products containing other aryl-sulphone-aroylamino groups, with or without other acylamino groups which may be non-aromatic.  This subject-matter does not appear in the Specification as accepted.